|Número de publicación||US4663216 A|
|Tipo de publicación||Concesión|
|Número de solicitud||US 06/739,818|
|Fecha de publicación||5 May 1987|
|Fecha de presentación||31 May 1985|
|Fecha de prioridad||18 Jun 1984|
|Número de publicación||06739818, 739818, US 4663216 A, US 4663216A, US-A-4663216, US4663216 A, US4663216A|
|Inventores||Takashi Toyoda, Akira Akimoto, Masaaki Yamanaka, Yonetarou Kobayasi|
|Cesionario original||Oji Yuka Goseishi Co., Ltd.|
|Exportar cita||BiBTeX, EndNote, RefMan|
|Citas de patentes (5), Citada por (67), Clasificaciones (33), Eventos legales (5)|
|Enlaces externos: USPTO, Cesión de USPTO, Espacenet|
This invention relates to a synthetic paper having excellent paper supply property and ink transfer property and free from curling, which can provide the advantage that multicolor prints thereon have a high gloss.
Synthetic papers, or probably more accurately termed paper-like sheets, comprising a biaxially stretched film of polypropylene as a base layer and monoaxially stretched films of polypropylene containing 8 to 65% by weight of an inorganic fine powder formed on both surfaces of the base layer as paper-like layers have been proposed and come into commercial acceptance in place of conventional pulp papers as described in, for example, Japanese Patent Publication No. 40794/71 and Japanese Patent Application (OPI) Nos. 141339/81 and 118437/81 (the term "OPI" as used herein refers to a "published unexamined Japanese patent application").
Such synthetic papers have fine pores around the nuclei of the inorganic fine powder and numerous long cracks on both surfaces. They are light in weight and have excellent drying property of a printing ink, adhesion of a printing ink, writing property with a pencil and waterproofness.
To impart better offset printing property, those synthetic papers are used after their surfaces are coated with an aqueous solution of an acrylic copolymer, polyethyleneimine, etc., in an amount of a solids content of from 0.005 to 1 g/m2 and dried as described in, for example, Japanese Patent Application (OPI) Nos. 10624/75, 161478/75, 40883/73 and 149363/82.
The synthetic papers having such a coated resin layer are used as labels on containers holding liquids such as motor oil and shampoo, blanks of fancy foods, and art paper for maps and posters.
The surfaces of those synthetic papers are rough (a Bekk index, measured in accordance with JIS P-8119, of from 100 to 2,000 seconds) because the paper-like layer is a stretched film of a thermoplastic resin containing an inorganic fine powder and the coated resin layer is as thin as 0.01μ or less.
Papers for posters are required to be offset-printed in multicolors with excellent gloss. In particular, in those posters which advertise or publicize package tours and motion pictures or promote the sales of records, automobiles, carbonated drinks, etc., using young female models, multicolor offset prints of strong gloss are preferred in order to create a bright and light-hearted atmosphere.
Such posters have been previously produced by applying offset multicolor prints to the surface of a synthetic paper having the above-described coated resin layer, coating an isocyanate type primer on the printed surface, and then laminating a transparent polyvinyl chloride film onto the primer layer. Because of the surface smoothness of the polyvinyl chloride film on the surface, those posters look as if prints of excellent gloss were made.
The production of those posters having a laminated layer of polyvinyl chloride additionally requires a transportation expense because they come through both printers and laminaters. To the users, direct delivery of the posters from the printers is advantageous in regard to both time and cost.
As a result of various investigations to provide a synthetic paper which can be directly offset-printed in high gloss and has satisfactory paper supply property, paper discharge property, paper-like feel and anti-curling property, it has been found that the synthetic paper having a specific structure can meet those requirements.
Accordingly, an object of the present invention is to provide a synthetic paper printable in high gloss, the synthetic paper comprising (1) a support of a multilayer film comprising a base layer (1a) of a biaxially stretched film of a thermoplastic resin, a surface layer (1b) and a back layer (1c), (1b) and (1c) each being a monoaxially stretched film of a thermoplastic resin containing from 8 to 65% by weight of an inorganic fine powder, (2) a layer of a transparent film of a thermoplastic resin free from an inorganic fine powder formed on the surface layer (1b) of the support, and (3) a primer of a material selected from the group consisting of polyethyleneimine, poly(ethyleneimine-urea), ethyleneimine-adducts of polyamine polyamides, epichlorohydrin-adducts of polyamine polyamides and quaternary nitrogen-containing polymers.
Figure is a cross-sectional view of the synthetic paper according to the present invention.
In the synthetic paper of this invention as shown in the drawing, the support (1) has a multilayer structure comprising (1a) a base layer of a biaxially stretched film of a thermoplastic resin and surface and back layers (1b) and (1c) of a monoaxially stretched film of a thermoplastic resin containing from 8 to 65% by weight of an inorganic fine powder. The support (1) can be produced by the methods described in the specifications of the above-described Japanese Patent Publication No. 40794/71, Japanese Patent Application (OPI) Nos. 141339/81 and 118437/81 and Japanese Patent Application No. 67842/81.
Specifically, this multilayer structure may be produced, for example, by stretching a film of a thermoplastic resin containing from 0 to 50% of an inorganic fine powder in one direction at a temperature lower than the melting point of the resin, laminating a molten film of a thermoplastic resin containing from 8 to 65% by weight of an inorganic fine powder onto both surfaces of the resulting monoaxially stretched film, and thereafter stretching the laminated film in a direction at right angles to the above-described direction. In the resulting product, the paper-like layer is a film which is monoaxially oriented and having numerous fine pores, and the base layer is oriented biaxially.
Such a three-layer structure is the simplest structure of the support, and another resin layer may be present between the paper-like layer and the base layer as described in, for example, Japanese Patent Application (OPI) No. 181829/82.
The base layer (1a) of the biaxially stretched film in the support (1) contributes to a balance between the longitudinal and transverse strengths of the synthetic paper. The paper-like layers (1b, 1c) of the monoaxially stretched film serve to present a paper-like feel. If the paper-like layer is biaxially oriented, it has a pearlescent luster and is far from a paper-like feel.
Examples of the thermoplastic resin include polyolefin resins (such as polyethylene, polypropylene, ethylene/propylene copolymer, and ethylene/vinyl acetate copolymer), poly(4-methylpentene-1), polystyrene, polyamides, polyethylene terephthalate, a partially hydrolyzed product of ethylene/vinyl acetate copolymer, ethylene/acrylic acid copolymer, salts of ethylene/acrylic acid copolymer, vinylidene chloride copolymers (such as vinyl chloride/vinylidene chloride copolymer), and blends of those polymers. Polypropylene and polyethylene are especially preferred because of their excellent waterproofness and resistance to chemicals. When polypropylene is used as the base layer, it is preferable to incorporate from 3 to 25% by weight of a resin having a lower melting point than the polypropylene, such as polyethylene, polystyrene or ethylene/vinyl acetate copolymer, in order to improve its stretchability.
The adhesion between the base layer and the paper-like layer is higher when the thermoplastic resins constituting those layers are the same kind. The stretching of the support (1) becomes easy if a resin having a higher melt index (measured in accordance with, for example, JIS K-6758, JIS K-6780) than the resin of the base layer is used.
Examples of the inorganic fine powder are fine powders of calcium carbonate, silica, diatomaceous earth, talc, titanium oxide and barium sulfate having a particle diameter of from about 0.03 to 16 microns.
The stretch ratio is preferably from 4 to 10 both in the longitudinal and transverse directions. The stretching temperature is from 150° to 162° C. for homopolypropylene (melting point: 164°-167° C.), from 110° to 120° C. for high density polyethylene (melting point: 121° to 124° C.), and from 104° to 115° C. for polyethylene terephthalate (melting point: 246°-252° C.). The stretching speed is from about 50 to 350 m/min.
If the stretch ratio, the stretching temperature, the stretching speed and the content of the inorganic fine powder are selected such that the smoothness (Bekk index) of the paper-like layers (1b, 1c) becomes 3,000 seconds or less, preferably 2,000 seconds or less, the paper-like layers can permit writing with a pencil, and the supply and discharge of the resulting synthetic paper are improved.
The transparent thermoplastic resin film layer (2) free from an inorganic fine powder is formed on the paper-like layer (1b) of the support. The paper-like layer (1c) on the opposite side becomes a back layer of the synthetic paper. The thermoplastic resin forming the transparent film layer (2) may, for example, be low density polyethylene, polypropylene, polyethylene terephthalate, polyamides, etc. The transparent film layer (2) can be formed on the support (1) by, for example, a method which comprises coating a polyurethane type or polyester type primer on the surface of the paper-like layer (1b) of the support (1) and then extruding a molten film of the thermoplastic resin (2) onto the primer by an extrusion dry laminating technique; or by a method which comprises laminating a molten laminated film of the thermoplastic resin containing from 8 to 65% by weight of the inorganic fine powder for formation of the paper-like layer (1b) and the thermoplastic resin containing no inorganic fine powder for formation of the transparent film layer (2), extruded from a coextrusion die, onto one surface of the longitudinally stretched film (1a) as the base layer in the production of the support (1), extrusion-laminating a molten film of the thermoplastic resin containing from 8 to 65% by weight of the inorganic fine powder for the formation of the back layer (1c) of the support (1), and stretching the laminated film transversely.
The example of the polyurethane type primer is EL-150 (trade name) of Toyo Morton Co., Ltd., and the example of the polyester type elastomer is AD-503 (trade name) of the same company. The primer is coated at a rate of from 0.5 to 5 g/m2.
Generally, the transparent resin film layer (2) has a thickness of from 2 to 20 microns, and the support (1) has a thickness of from 60 to 400 microns. It is important that the transparent film (2) has a smoothness (Bekk index) of at least 6,000 seconds. As the Bekk index is higher, prints of higher gloss can be obtained, and the ink transfer property is better. Better ink transfer property leads to a lesser amount of ink used.
The transparent film (2) has excellent smoothness and therefore excellent ink transfer property. However, since its ink adhesion is poor, its surface is treated with a primer. The primer is selected from polyethyleneimine, poly(ethyleneimine-urea), ethyleneimine adducts of polyamine polyamides, epichlorohydrin adducts of polyamine polyamides and quaternary nitrogen-containing polymers. An alkali metal salt or an alkaline earth metal salt may be incorporated in the primer in order to promote the drying of ink. When the transparent film layer (2) is composed of a homopolymer, the primer (3) composed of the following components (A), (B), (C) and (D) gives an offset multicolor print (4) having excellent adhesion.
(A) A quaternary nitrogen-containing polymer: 100 parts by weight
(B) A polyimine compounds selected from polyethyleneimine poly(ethyleneimine-urea) and ethyleneimine adducts of polyamidepolyamines.
20 to 500 parts by weight
(C) An epichlorohydrin adduct of a polyamine polyamide. 20 to 500 parts by weight
(D) An alkali metal salt or an alkaline earth metal salt. 5 to 50 parts by weight
The acrylic polymer of component (A) is a water-soluble quaternary nitrogen-containing polymer having antistatic function. The term "quaternary" as used herein is to be understood as encompassing the term "amphoteric".
Such a quaternary nitrogen-containing polymer can be prepared by the polymerization of the corresponding nitrogen-containing monomer and as required, by quaternization of the resulting tertiary nitrogen-containing polymer.
Suitable examples of the nitrogen-containing monomer in the present invention are as follows. ##STR1##
In the above formulae, R1 represents hydrogen or a methyl group; R2 and R3 each represents a lower alkyl group preferably having 1 to 4 carbon atoms and more preferably having 1 or 2 carbon atoms; R4 represents a saturated or unsaturated alkyl group having 1 to 22 carbon atoms; X.sup.⊖ represents a counter anion of quaternized N.sup.⊕ (for example, a halide especially a chloride); M represents an alkali metal ion (especially a sodium, potassium or lithium ion); and A represents an alkylene group having 2 to 6 carbon atoms.
Needless to say, the quaternary nitrogen-containing monomers (ii), (iv), (vi) and (vii) can be caused to be present in the polymer by polymerizing their precursors (i), (iii) and (v), respectively, and quaternizing the products with a cationizing agent such as an alkyl halide, dimethylsulfuric acid or a monochloroacetic acid ester.
In the present invention, the primer must be water-soluble, but it is not desired to be excessively water-soluble. Hence, the quaternary nitrogen-containing polymer is desirably a copolymer with a hydrophobic monomer. Examples of the hydrophobic monomer are styrene, nucleus- or side chain-substituted products of styrene, acrylic or methacrylic acid esters, and vinyl halides.
Especially suitable polymers (A) are composed of the following components (a) to (c).
______________________________________(a) Monomer (i) to (vii) 20 to 40% by weight(b)##STR2## 6 to 80% by weight (R.sup.1 is hydrogen or a methyl group, and R.sup.5 is an alkyl group having 1 to 18 carbon atoms)(c) Another hydrophobic vinyl monomer 0 to 20% by weight______________________________________
The most suitable acrylic polymer of component (A) is a polymer wherein the monomer (a) is the monomer (vi) and X.sup.⊖ is Cl.sup.⊖.
Polyethyleneimine, a copolymer of ethyleneimine and urea [poly(ethyleneimine-urea)] or the ethyleneimine adduct of polyamine polyamide in component (B) is a water-soluble polymer.
The degrees of polymerization of those polymers, the content of the urea units in poly(ethyleneimineurea), and the amount of ethyleneimine added in the adduct are not limited in particular so long as these factors serve to achieve an improvement in the adhesion of a printing ink.
The polyamine polyamide/epichlorohydrin adduct as the component (C) of the primer is a water-soluble cationic thermosetting resin obtained by reacting a polyamide obtained from a polyalkylenepolyamine and a saturated dibasic carboxylic acid having from 3 to 10 carbon atoms, with epichlorohydrin. The details of this resin are described in Japanese Patent Publication No. 3547/60. Specific examples of the saturated dibasic carboxylic acid having from 3 to 10 carbon atoms are dicarboxylic acids having from 4 to 8 carbon atoms, especially adipic acid. Specific examples of the polyalkylenepolyamine are polyethylenepolyamines, especially ethylenediamine, diethylenetriamine and triethylenetetramine. Diethylenetriamine is especially preferred. The mole ratio of the polyalkylene polyamine to dibasic acid in the polyamide forming reaction is usually from 0.9:1 to 1.2:1. In the reaction of the polyaminepolyamide with epichlorohydrin, epichlorohydrin is usually used in an amount of from about 0.5 to 1.8 moles per mole of the secondary amino groups in the polyamides.
The water-soluble alkali metal salt or alkaline earth metal salt as component (D) has an effect of increasing the antistatic function of the primer and promoting the drying of an offset printing ink. Since, however, the presence of a water-soluble inorganic salt reduces the water resistant adhesion of ink, its presence in excessively large amounts is undesirable.
Examples of preferred water-soluble inorganic salts include sodium carbonate, potassium carbonate, sodium hydrogencarbonate, sodium sulfite and other alkaline salts; and sodium chloride, sodium sulfate, sodium nitrate and other neutral salts.
The coating composition comprising the primers (A), (B) and (C) and the water-soluble inorganic salt (D) is used as an aqueous solution having a concentration of 0.5 to 3% by weight. The solution is coated on the transparent film (2) by such a coating means as a roll, a sprayer or a brush at a rate of 0.01 to 1.0 g/m2 (solids), and dried.
The primer layer (3) of the synthetic paper thus obtained has a smoothness nearly the same as that of the transparent film (2) as represented by its Bekk index of from 6,000 to 30,000 seconds.
The synthetic resin thus obtained has excellent ink transfer property and adhesion of an offset printing ink. Its printed surface has a high gloss.
Since the primer layer (3) and the transparent film layer (2) of this synthetic paper cover the paper-like layer (1b) containing the fine powder, this synthetic paper is free from the problem of dropping of the inorganic fine powder from the paper-like layer which is called "paper powder trouble". Accordingly, this synthetic paper is useful for drawing a flow chart or a poster for feasting the eyes of working personnel which is pasted on the wall of a room where dirt and dust are undesired, for example, in a room for production of IC or LSI.
The synthetic paper of the present invention can be printed not only by offset printing, but also by gravure printing, flexographic printing and screen printing.
The following examples illustrate the present invention in greater detail.
(1) A mixture of 80% by weight of polypropylene having a melt index (MI) of 0.8 and 8% by weight of high density polyethylene was mixed with 12% by weight of calcium carbonate having an average particle diameter of 1.5 microns (C), and the mixture was kneaded in an extruder kept at 270° C. and extruded into a sheet. The extruded sheet was cooled by a cooling device to obtain an unstretched sheet. The sheet was heated to 140° C. and then stretched to 5 times in the longitudinal direction. (2) Polypropylene (A) having an MI of 4.0 and a composition (B) composed of 55% by weight of polypropylene having an MI of 4.0 and 45% by weight of calcium carbonate having an average particle diameter of 1.5 microns were melt-kneaded in separate extruders, and laminated within a die and coextruded. The extruded sheet was laminated onto the stretched sheet (1) so that the (A) side of the coextruded sheet was located outside. Then, a composition (E) composed of 49% by weight of polypropylene having an MI of 4.0, 5% by weight of maleic acid-modified polypropylene having a maleic acid content of 0.5% by weight, and 46% by weight of calcium carbonate having an average particle diameter of 1.5 microns (the amount of the modifying maleic acid monomer per 100 parts by weight of the filler was 0.05 part by weight), which was melt-extruded in an extruder kept at 270° C., and a composition (D) composed of 50% by weight of polypropylene having an MI of 4.0 and 50% by weight of calcium carbonate having an average particle diameter of 1.5 microns, which was melt-kneaded in another extruder kept at 270° C., were laminated in a die and coextruded onto the other side of the 5:1 stretched sheet so that the layer (E) containing the modified polypropylene was located outside. The 5-layer laminate was then heated to 155° C., and stretched to 7.5 times in the transverse direction to obtain a 5-layer sheet.
(3) The surface of the 5-layer sheet was subjected to a corona discharge treatment to obtain a 5-layer sheet composed of the layers (A), (B), (C), (D) and (E) having a thickness of 5, 25, 50, 25 and 5 microns, respectively.
The surface (A) of this 5-layer structure had a Bekk index of 8,000 seconds.
A 5-layer structure having a surface Bekk index of 1,500 seconds was produced in the same manner as in Production Example 1 except that the composition of (A) was changed as follows:
______________________________________Polypropylene 96% by weightMaleic acid-modified polypropylene 1% by weightCalcium carbonate 3% by weight______________________________________
A resin composition composed of 80% by weight of polypropylene having an MI of 4.0, 4% by weight of high density polyethylene and 16% by weight of calcium carbonate was extruded at 270° C., cooled, stretched to 5 times longitudinally at 140° C., again heated to 155° C., then stretched transversely to 5.2 times, subjected to a corona discharge treatment, and annealed at 160° C. to give a synthetic paper having a thickness of 110 microns.
The synthetic paper had a pearlescent luster and a Bekk index of 10,500 seconds.
A polyester type primer, "AD-503" (trade name) made by Toyo Morton Co., Ltd., was coated at a rate of 1 g/m2 on one surface of each of the supports obtained in Production Examples 2 and 3. Propylene homopolymer having an MI of 4.0 or a composition composed of the propylene homopolymer and calcium carbonate having a particle diameter of 1.5 microns in the proportions indicated in Table 1 was extruded at 270° C. into a film form onto the primer-coated surface and laminated onto the support by a roll. The assembly laminate was cooled to 60° C. and its surface was subjected to a corona discharge treatment to obtain a laminate having a film layer (thickness: 10 microns) with the smoothness shown in Table 1.
Aqueous coating solutions of the various compositions shown in Table 1 were each coated at a rate of 0.05 g/m2 as solids on the surface of the polypropylene film in the laminate obtained in Production Example 1, and dried at 20° C. to produce synthetic papers for printing.
Offset printing in four colors (black, blue, red and yellow) was performed on the polypropylene film surface side of each of those synthetic papers using an offset printing ink "TSP-400" (trade name) produced by Toyo Ink Mfg., Co., Ltd. on an offset 4-color printing press made by Komori Printing Press Co., Ltd. The ink transfer property, adhesion of the ink, continuous offset printing property, the gloss of the prints, the supply and discharge property of the synthetic papers, and the presence or absence of plate staining were evaluated by the following methods. The results obtained are shown in Table 1 below.
Ink Transfer Property:
A halftone dot portion of each color was enlarged to 30 times by a magnifying glass, and the reproducibility of the dot was visually evaluated.
Dot reproduction rate:
100-75%: Good (o)
75-50%: Slightly poor (Δ)
50-0% Poor (x)
An adhesive tape, "Cellotape" (trade name) made by Nichiban Co., Ltd., was adhered strongly to the printed surface and quickly peeled along the printed surface. The degree of ink separated from the paper surface was visually evaluated.
Ink remaining ratio:
100-95%: Good (o)
95-80%: Slightly poor (Δ)
80-0%: Poor (x)
Continuous Offset Printing Property:
5,000 copies were continuously printed, and the ink edge pile on the blanket and the whiteness of the blanket were compared with those before the printing. The printed copy obtained immediately after the start of printing and that obtained after the continuous printing were compared, and their halftone dot reproducibilities were visually evaluated.
State of the blanket:
Same as that before the printing (o)
Slight difference (Δ)
Great difference (x)
Gloss of the Print:
The gloss of the solid printed surface was measured using a glossmeter made by Suga Testing Device Co., Ltd. The state of light reflection of the entire print was visually observed.
State of light reflection of the entire print:
Slightly good (Δ)
Supply-Discharge Property of the Synthetic Paper:
The state of supply of the synthetic paper from the feeder portion of a printing press was evaluated by visually observing paper separation and the state of paper registering at the holding portion and the state of paper dropping at the paper discharge portion.
The state of staining of the printing plate by ink during continuous printing of 5,000 copies was visually evaluated.
Synthetic papers were produced in the same manner as in Example 1 except that the supports obtained in Production Examples 2 and 3 having no propylene homopolymer film layer were used.
The results obtained are shown in Table 1 below.
TABLE 1__________________________________________________________________________ Coating Agent Composition (parts by weight) (A) Laminated Structure Quaternary (D) Production Bekk N--Containing (B) Inorganic AmountExample Example Index (sec) Acrylic Polymer Polyethyleneimine (C) Salt Coated__________________________________________________________________________ (g/m.sup.2)1-A 1 8,000 "CHEMISTAT 500" "POLYMIN P" (25) "AF-100" Na.sub.2 CO.sub.3 0.05 (100) (25) (10)1-B " " "ST-1000" (100) "POLYMIN SN" (50) "AF-100" Na.sub.2 CO.sub.3 " (50) (10)1-C " " "ST-1100" (100) "POLYMIN SN" (30) "KYMENE" Na.sub.2 CO.sub.3 " (30) (15)1-D " " "CHEMISTAT 6200" "POLYMIN P" (20) -- Na.sub.2 CO.sub.3 " (100) (10)1-E " " "GOSEFIMER "POLYMIN P" (120) "AF-100" Na.sub.2 SO.sub.3 " C-670" (150) (100) (10)1-F " " "ST-1100" (200) "POLYMIN SN" (100) "AF-100" Na.sub.2 CO.sub.3 0.1 (100) (20)1-G " " "CHEMISTAT 5500" "POLYMIN SN" (200) "AF-100" Na.sub.2 CO.sub.3 " (100) (200) (20)2 4 7,500 "CHEMISTAT 5500" "POLYMIN SN" (50) "AF-100" Na.sub.2 CO.sub.3 0.05 (100) (50) (20)3 5 8,900 "CHEMISTAT 5500" "POLYMIN SN" (50) "AF-100" Na.sub.2 CO.sub.3 " (100) (50) (20)Comp. Ex. 1 2 3,500 "CHEMISTAT 5500" " "AF-100" Na.sub.2 CO.sub.3 " (100) (50) (20)Comp. Ex. 2 3 10,500 "CHEMISTAT 5500" " "AF-100" Na.sub.2 CO.sub.3 " (100) (50) (20)__________________________________________________________________________ Evaluation of the Synthetic Paper Ink Transfer Continuous Printing Paper Supply-Example Property Ink Adhesion Gloss of Print Property Discharge Property Plate Remarksg__________________________________________________________________________1-A Δ˜o o o 5,000 o o1-B o o o 5,000 o o or more1-C o o o 5,000 o o or more1-D Δ˜o Δ˜o o 4,500 o o1-E Δ˜o o o 4,500 o o1-F o o o 5,000 o o or more1-G Δ˜o o o 4,500 o Δ˜o2 o o o 4,500 o o Slight curling3 o o o 4,500 o o Slight curlingComparative o o x 1,000 o oExample 1Comparative Δ oΔ Δ 3,000 o oExample 2__________________________________________________________________________
In Table 1, the compounds given by trade names are produced by the following manufacturers.
"CHEMISTAT 5500" and "CHEMISTAT 6200": Sanyo Chemical Co., Ltd.
"ST-1000" and "ST-1100": Mitsubishi Yuka Fine Chemicals Co., Ltd.
"GOSEFIMER C-670": Nippon Gosei Kagaku Co., Ltd.
"POLYMIN P" and "POLYMIN SN": BASF A.G.
"AF-100" Arakawa Chemical Co., Ltd.
"KYMENE": Dick Hercules Co.
While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.
|Patente citada||Fecha de presentación||Fecha de publicación||Solicitante||Título|
|US3799828 *||12 Ago 1971||26 Mar 1974||Mitsubishi Petrochemical Co||Synthetic papers and the method of making the same|
|US4341880 *||20 Feb 1981||27 Jul 1982||Oji Yuka Goseishi Kabushiki Kaisha||Resin compositions of improved hue|
|US4420530 *||8 Mar 1982||13 Dic 1983||Oji Yuka Goseishi Kabushiki Kaisha||Coating agents and thermoplastic resin films coated therewith|
|US4472227 *||4 May 1982||18 Sep 1984||Oji Yuka Goseishi Kabushiki Kaisha||Process for producing oriented composite polyolefin resin films|
|GB1403237A *||Título no disponible|
|Patente citante||Fecha de presentación||Fecha de publicación||Solicitante||Título|
|US4777077 *||23 Sep 1985||11 Oct 1988||Dai Nippon Insatsu Kabushiki Kaisha||Base film for three-dimensional conformability|
|US4906526 *||30 Nov 1988||6 Mar 1990||Oji Yuka Goseishi Co., Ltd.||Thermoplastic resin film having improved printability|
|US5215817 *||18 Nov 1991||1 Jun 1993||Mobil Oil Corporation||Computer printable coated films|
|US5268349 *||30 Oct 1992||7 Dic 1993||Oji Yuka Goseishi Co., Ltd.||Recording material|
|US5364695 *||2 Jul 1990||15 Nov 1994||Gurewitz Richard M||Thermoplastic film from polyethylene having improved surface adhesion and method of making thereof|
|US5489471 *||21 Sep 1994||6 Feb 1996||Oji Yuka Goseishi Co., Ltd.||White resin film with excellent printability|
|US5672409 *||15 Nov 1993||30 Sep 1997||Toray Industries, Inc.||Polyester film reflector for a surface light source|
|US5834063 *||3 Mar 1997||10 Nov 1998||Nisshinbo Industries, Inc.||Recording medium and method of producing the same|
|US5834098 *||19 Jun 1997||10 Nov 1998||Oji-Yuka Synthetic Paper Co., Ltd.||Laminate with excellent printability|
|US5846637 *||7 May 1997||8 Dic 1998||Xerox Corporation||Coated xerographic photographic paper|
|US5871833 *||13 Ene 1997||16 Feb 1999||Oji-Yuka Synthetic Paper Co., Ltd.||Forgery-preventive fretwork paper|
|US5885929 *||17 Jun 1997||23 Mar 1999||Eastman Kodak Company||Reusable donor layer containing dye wells for thermal printing|
|US5897961 *||7 May 1997||27 Abr 1999||Xerox Corporation||Coated photographic papers|
|US5908723 *||7 May 1997||1 Jun 1999||Xerox Corporation||Recording sheets|
|US6033771 *||16 Jul 1997||7 Mar 2000||Mobil Oil Corporation||WVTR film using wax in combination with a cavitated tie layer|
|US6171702 *||17 Jul 1998||9 Ene 2001||Xerox Corporation||Coated substrates|
|US6177222||12 Mar 1998||23 Ene 2001||Xerox Corporation||Coated photographic papers|
|US6238785 *||3 Oct 1997||29 May 2001||Oji-Yuka Synthetic Paper Co., Ltd.||Thermoplastic resin film with excellent printability|
|US6319591||26 Mar 1999||20 Nov 2001||Xerox Corporation||Ink jet recording substrates|
|US6326085||2 Nov 2000||4 Dic 2001||Xerox Corporation||Coated photographic papers|
|US6340530 *||28 Abr 2000||22 Ene 2002||Honeywell International Inc.||Matte coextruded nylon film for book covers|
|US6416874||7 Nov 2001||9 Jul 2002||Xerox Corporation||Coated photographic papers|
|US6444294||27 Jul 2000||3 Sep 2002||Xerox Corporation||Recording substrates for ink jet printing|
|US6461706 *||17 Abr 1998||8 Oct 2002||Avery Dennison Corporation||Multilayer films and labels|
|US6495243||27 Jul 2000||17 Dic 2002||Xerox Corporation||Recording substrates for ink jet printing|
|US6514660||29 Oct 2001||4 Feb 2003||Eastman Kodak Company||Polyethyleneimine primer for imaging materials|
|US6589621 *||1 Jul 1998||8 Jul 2003||Dow Global Technologies Inc.||Thermally stable polyetheramines|
|US6749982||27 Sep 2002||15 Jun 2004||Eastman Kodak Company||Imaging member with polyester base|
|US6800363 *||29 Ago 2002||5 Oct 2004||Toray Plastics, Inc.||Polyolefin oil resistant film using porous particles|
|US6835462||6 Sep 2002||28 Dic 2004||Avery Dennison Corporation||Conformable and die-cuttable biaxially oriented films and labelstocks|
|US6852407||29 Mar 2001||8 Feb 2005||Idemitsu Petrochemical Co., Ltd.||Polyolefin-based sheet, display sheet comprising the same, package sheet, transparent recording sheet, cosmetic sheet, emblem sheet, decorative sheet, and coating material for polyolefin resin for use in these|
|US6855411 *||5 Sep 2002||15 Feb 2005||Toray Plastics (America), Inc.||Polyolefin oil resistant film using void initiating solid particles|
|US6881492||27 Sep 2002||19 Abr 2005||Eastman Kodak Company||Primer composition for polyesters|
|US7217463||26 Jun 2003||15 May 2007||Avery Dennison Corporation||Machine direction oriented polymeric films and methods of making the same|
|US7410706||12 May 2005||12 Ago 2008||Avery Dennison Corporation||Machine direction only oriented films|
|US8105686||17 Jul 2007||31 Ene 2012||Avery Dennison Corporation||Asymmetric multilayered polymeric film and label stock and label thereof|
|US8211507 *||27 Ago 2004||3 Jul 2012||Yupo Corporation||Method for producing thermoplastic resin film|
|US9302418 *||23 Ago 2006||5 Abr 2016||Yupo Corporation||Resin film and method for producing same, printed matter, label and resin molded article|
|US9636895||20 Jun 2007||2 May 2017||Avery Dennison Corporation||Multilayered polymeric film for hot melt adhesive labeling and label stock and label thereof|
|US9662867||13 Jun 2007||30 May 2017||Avery Dennison Corporation||Conformable and die-cuttable machine direction oriented labelstocks and labels, and process for preparing|
|US9676532||13 Ago 2013||13 Jun 2017||Avery Dennison Corporation||Packaging reclosure label for high alcohol content products|
|US20030049475 *||29 Ago 2002||13 Mar 2003||Tien-Kuei Su||Polyolefin oil resistant film using porous particles|
|US20030113535 *||6 Sep 2002||19 Jun 2003||Sun Edward I.||Conformable and die-cuttable biaxially oriented films and labelstocks|
|US20040063819 *||27 Sep 2002||1 Abr 2004||Eastman Kodak Company||Primer composition for polyesters|
|US20050085579 *||27 Ago 2004||21 Abr 2005||Yupo Corporation||Method for producing thermoplastic resin film|
|US20050214558 *||12 May 2005||29 Sep 2005||Rodick Ronald G||Conformable holographic labels|
|US20070098963 *||27 Oct 2005||3 May 2007||Xiaoqi Zhou||Toner receiving compositions for electrophotographic toner receiving systems|
|US20080280113 *||23 Ago 2006||13 Nov 2008||Yupo Corporation||Resin Film and Method for Producing Same, Printed Matter, Label and Resin Molded Article|
|CN1058028C *||5 Oct 1994||1 Nov 2000||王子油化合成纸株式会社||White resin film with excellent printability|
|CN102700283A *||28 May 2012||3 Oct 2012||绵阳龙华薄膜有限公司||Laser marking film|
|EP0458147A2 *||10 May 1991||27 Nov 1991||Hoechst Celanese Corporation||Polymeric film coated in-line with polyethyleneimine|
|EP0458147B1 *||10 May 1991||21 Ago 1996||Hoechst Celanese Corporation||Polymeric film coated in-line with polyethyleneimine|
|EP0470760A2||31 Jul 1991||12 Feb 1992||BXL Plastics Limited||Composite plastics film or sheet|
|EP0540020A1 *||30 Oct 1992||5 May 1993||Oji Yuka Goseishi Co., Ltd.||Recording paper|
|EP0779162A2 *||28 Nov 1996||18 Jun 1997||Oji-Yuka Synthetic Paper Co., Ltd.||Recording sheet having a laminated support|
|EP0779162A3 *||28 Nov 1996||1 Jul 1998||Oji-Yuka Synthetic Paper Co., Ltd.||Recording sheet having a laminated support|
|EP0796730A2 *||31 Ene 1997||24 Sep 1997||Oji-Yuka Synthetic Paper Co., Ltd.||Forgery-preventive fretwork paper and use thereof|
|EP0796730A3 *||31 Ene 1997||1 Dic 1999||Oji-Yuka Synthetic Paper Co., Ltd.||Forgery-preventive fretwork paper and use thereof|
|EP0813955A2 *||13 Jun 1997||29 Dic 1997||Oji-Yuka Synthetic Paper Co., Ltd.||Laminate with excellent printability|
|EP0813955A3 *||13 Jun 1997||22 Ago 2001||Yupo Corporation||Laminate with excellent printability|
|EP1275684A1 *||29 Mar 2001||15 Ene 2003||IDEMITSU PETROCHEMICAL CO. Ltd.||Polyolefin-based sheet, display sheet comprising the same, package sheet, transparent recording sheet, cosmetic sheet, emblem sheet, decorative sheet, and coating material for polyolefin resin for use in these|
|EP1275684A4 *||29 Mar 2001||16 Jul 2003||Idemitsu Petrochemical Co||Polyolefin-based sheet, display sheet comprising the same, package sheet, transparent recording sheet, cosmetic sheet, emblem sheet, decorative sheet, and coating material for polyolefin resin for use in these|
|EP1403701A2 *||15 Sep 2003||31 Mar 2004||Eastman Kodak Company||Imaging member with polyester base|
|EP1403701A3 *||15 Sep 2003||21 Abr 2004||Eastman Kodak Company||Imaging member with polyester base|
|EP1938968A1 *||23 Ago 2006||2 Jul 2008||Yupo Corporation||Resin film and method for producing same, printed matter, label and resin molded article|
|EP1938968A4 *||23 Ago 2006||28 Oct 2009||Yupo Corp||Resin film and method for producing same, printed matter, label and resin molded article|
|WO1999003673A1 *||1 Jul 1998||28 Ene 1999||Mobil Oil Corporation||Improved wvtr film using wax in combination with a cavitated tie layer|
|Clasificación de EE.UU.||428/212, 428/409, 428/335, 428/476.3, 428/474.4, 428/323, 428/476.9|
|Clasificación internacional||B32B27/00, B41M5/52, B32B27/20, B41M5/00, B41M5/50, C08J7/04|
|Clasificación cooperativa||B41M5/5254, B32B27/08, B32B2307/412, B32B2307/518, B32B27/18, B32B2307/516, Y10T428/31757, Y10T428/3175, Y10T428/31725, B32B27/20, Y10T428/24942, Y10T428/31, B41M5/508, Y10T428/25, B41M5/502, Y10T428/264, B41M5/52|
|Clasificación europea||B41M5/52K, B41M5/50B, B32B27/20|
|5 Ene 1987||AS||Assignment|
Owner name: OJI YUKA GOSEISHI CO., LTD., 5-1, MARUNOUCHI 1-CHO
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:TOYODA, TAKASHI;AKIMOTO, AKIRA;YAMANAKA, MASAAKI;AND OTHERS;REEL/FRAME:004649/0448
Effective date: 19850517
Owner name: OJI YUKA GOSEISHI CO., LTD., JAPAN
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:TOYODA, TAKASHI;AKIMOTO, AKIRA;YAMANAKA, MASAAKI;AND OTHERS;REEL/FRAME:004649/0448
Effective date: 19850517
|22 Oct 1990||FPAY||Fee payment|
Year of fee payment: 4
|26 Sep 1994||FPAY||Fee payment|
Year of fee payment: 8
|24 Dic 1997||AS||Assignment|
Owner name: OJI-YUKA SYNTHETIC PAPER CO., LTD., JAPAN
Free format text: CHANGE OF NAME;ASSIGNOR:OJI YUKA GOSEISHI CO., LTD.;REEL/FRAME:008869/0166
Effective date: 19941201
|26 Oct 1998||FPAY||Fee payment|
Year of fee payment: 12